Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2645—Metals or compounds thereof, e.g. salts
  • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
  • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
  • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
  • C09K2200/0657—Polyethers

Definitions

• the present invention relates to a curable composition
• a curable composition comprising a polyoxyalkylene polymer having a silicon-containing functional group (hereinafter also referred to as “reactive silicon group”) capable of crosslinking by forming a siloxane bond, a filler and a curing catalyst.
• the present invention also relates to a curable composition which improves the staining property of the cured product thereof, ensures mechanical properties favorable for a sealant such as low stress and high elongation, and is satisfactory in workability.
• Reactive silicon group-containing polymers undergo crosslinking curing in the presence of moisture.
• a curable composition which contains a polymer having a main chain skeleton formed of a polyoxypropylene, has characteristics such that it is liquid at room temperature and turns into a rubbery elastic substance by curing, and is accordingly widely used as sealants for use in building construction.
• the bleeding of the plasticizers contained in the sealants may be cited.
• exclusion of the plasticizers leads to a problem that the physical properties of the cured product tend to be high in modulus and low in elongation, resulting in the quality degradation and other failures of the sealants.
• the average number of the reactive silicon groups contained in one molecule of the polyoxyalkylene polymer is decreased for the purpose of lowering the modulus of the plasticizer-free cured product, there occurs a problem that the proportion of the unreacted polyoxyalkylene polymers having absolutely no reactive silicon groups is increased, and such polyoxyalkylene polymers cause staining around joints and other failures, similarly to the plasticizers.
• a cured composition in which the proportion between a liquid component including a particular polyoxyalkylene polymer, a filler and a curing catalyst, and also having reactive silicon groups and a liquid component having no reactive silicon groups is set to fall within a particular range, is satisfactory in workability and the cured product obtained therefrom have mechanical properties, desirable for sealant, such as low staining, low stress and high elongation.
• the present invention provides:
• a curable composition comprising: a reactive silicon group-containing polyoxyalkylene polymer which is obtained by reacting a polyoxyalkylene polymer (A) having a molecular weight distribution of 1.6 or less, a number average molecular weight of 15,000 to 50,000, and 0.8 or more of reactive groups, on average, per molecule thereof with an organic compound (B) having in the molecule thereof a reactive silicon group and a functional group capable of reacting with the reactive groups of the polymer (A) in a proportion of 0.8 to 1.5 molecules of the organic compound (B), on average, per molecule of the component (A); a filler (C); and a curing catalyst (D).
• A polyoxyalkylene polymer having a molecular weight distribution of 1.6 or less, a number average molecular weight of 15,000 to 50,000, and 0.8 or more of reactive groups, on average, per molecule thereof with an organic compound (B) having in the molecule thereof a reactive silicon group and a functional group capable of reacting with the reactive groups
• the curable composition according to any one of (1) and (2) comprising 10 parts by weight or less of a plasticizer in relation to 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer described in (1) or comprising no plasticizer.
• the curable composition according to any one of (1) to (3), in which the reactive group of the component (A) is an alkenyl group, and the component (B) is an organic compound having one hydrosilyl group per molecule thereof as a functional group capable of reacting with the component (A).
• the curable composition according to any one of (1) to (3), in which the reactive group of the component (A) is an isocyanate group, and the component (B) is an organic compound having one amino group per molecule thereof as a functional group capable of reacting with the component (A), and
• the curable composition of the present invention is satisfactory in workability, and the cured product obtained therefrom are satisfactory in anti-staining property and have mechanical properties, desirable for sealant, such as low stress and high elongation.
• the molecular weight distribution and the number average molecular weight of the component (A) used in the present invention are 1.6 or less and 15,000 to 50,000, respectively, the main chain structure of the polyoxyalkylene polymer having 0.8 or more reactive groups, on average, per molecule thereof is a polymer having a structure represented by —R—O— as repeating unit, wherein R is a divalent alkylene group having 1 to 20 carbon atoms.
• the component (A) may be either a homopolymer in which all the repeating units are the same or a copolymer in which two or more types of repeating units are included.
• the component (A) may have one or more branch structures in the main chain thereof.
• R may include —CH 2 CH 2 —, —CH(CH 3 )CH 2 —, —CH(C 2 H 5 )CH 2 —, —C(CH 3 ) 2 CH 2 — and —CH 2 CH 2 CH 2 CH 2 —.
• —CH(CH 3 )CH 2 — is particularly preferable.
• the main chain skeleton of the polyoxyalkylene polymer as the component (A) is obtained, for example, by ring-opening polymerization of monoepoxide in the presence of an initiator and a catalyst.
• the initiator may include dihydric alcohols and polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, bisphenol A, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylolmethane, trimethylolpropane and pentaerythritol; and various oligomers having hydroxyl groups.
• dihydric alcohols and polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, bisphenol A, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, tri
• the monoepoxide may include: alkylene oxides such as ethylene oxide, propylene oxide, ⁇ -butylene oxide, ⁇ -butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide and ⁇ -methylstyrene oxide; alkyl glycidyl ethers such as methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether and butyl glycidyl ether; allyl glycidyl ethers; and aryl glycidyl ethers.
• alkylene oxides such as ethylene oxide, propylene oxide, ⁇ -butylene oxide, ⁇ -butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide and ⁇ -methylstyrene oxide
• alkyl glycidyl ethers such as methyl
• catalysts well known in the art may be used.
• examples of such catalysts may include: alkali catalysts such as KOH, NaOH and CsOH; acidic catalysts such as trifluoroborane-etherate; alumino-porphyrin metal complexes; and double metal cyanide complex catalysts such as zinc cobalt cyanide-glyme complex catalyst.
• alkali catalysts such as KOH, NaOH and CsOH
• acidic catalysts such as trifluoroborane-etherate
• alumino-porphyrin metal complexes such as zinc cobalt cyanide-glyme complex catalyst.
• double metal cyanide complex catalysts which scarcely cause side reactions is preferable because the Mw/Mn values of the products are small and the viscosities thereof become low to ensure the favorable workability; however, catalysts other than the double metal cyanide complex catalysts may also be used.
• the main chain skeleton of the oxyalkylene polymer can also be obtained by subjecting a hydroxyl group-terminated oxyalkylene polymer to a chain elongation with a difunctional or higher alkyl halide such as CH 2 Cl 2 and CH 2 Br 2 , in the presence of a basic compound such as KOH, NaOH, KOCH 3 or NaOCH 3 .
• a difunctional or higher alkyl halide such as CH 2 Cl 2 and CH 2 Br 2
• the molecular weight of the oxyalkylene polymer is preferably 15,000 to 50,000 in terms of the number average molecular weight, based on GPC, relative to polystyrene standard.
• the number average molecular weight is less than 15,000, unpreferably those components having no reactive silicon groups introduced thereinto bleed from the cured product, similarly to the plasticizers and the like, to cause staining around the cured product, and the cured product of the obtained reactive silicon group-containing oxyalkylene polymer become brittle.
• the number average molecular weight exceeds 50,000, unpreferably the oxyalkylene polymer becomes too high in viscosity to make the handling thereof difficult.
• the number average molecular weight is more preferably 17,000 to 40,000, and particularly preferably 20,000 to 30,000 for the purpose of ensuring the anti-staining property, attaining the mechanical properties and ensuring the workability.
• the Mw/Mn value of the oxyalkylene polymer is preferably 1.6 or less. When the Mw/Mn value exceeds 1.6, the viscosity of the oxyalkylene polymer unpreferably becomes too high to make the handling thereof difficult.
• the Mw/Mn value concerned is preferably 1.5 or less, and particularly preferably 1.4 or less for the purpose of ensuring the workability.
• R 1 is a hydrogen atom or a hydrocarbon group having 10 or less carbon atoms.
• the production method of the polyoxyalkylene polymer having, at the terminals thereof, the alkenyl groups represented by the general formulas (1) and (2) methods well known in the art may be used; examples of such methods may include a method in which a hydroxyl group-terminated polyoxyalkylene polymer is reacted with a compound having an alkenyl bond to make bonds with the compound through ether bonds, ester bonds, urethane bonds, carbonate bonds and the like.
• alkenyl groups are introduced through ether bonds
• alkenyl-containing compound represented by the general formula (3) or (4) may include: H 2 C ⁇ CH—CH 2 —Cl, H 2 C ⁇ CH—CH 2 —Br, H 2 C ⁇ C(CH 3 )—CH 2 —Cl , H 2 C ⁇ C(CH 3 )—CH 2 —Br, H 2 C ⁇ C(CH 2 CH 3 )—CH 2 —Cl, H 2 C ⁇ C(CH 2 CH 3 )—CH 2 —Br, H 2 C ⁇ C(CH 2 CH(CH 3 ) 2 )—CH 2 —Cl, H 2 C ⁇ C(CH 2 CH(CH 3 ) 2 )—CH 2 —Br, HC(CH 3 ) ⁇ CH—CH 2 —Cl and HC(CH 3 ) ⁇ CH—CH 2 —Br; wherein H 2 C ⁇ CH—CH 2 —Cl and H 2 C ⁇ C(CH 3 )—CH 2 —Cl are particularly preferable.
• alkenyl groups isocyanate compounds, carboxylic acids and epoxy compounds having the H 2 C ⁇ C(CH 3 )—CH 2 — group or the HC(CH 3 ) ⁇ CH—CH 2 — group may also be used, in addition to the above compounds.
• the organic compound as the component (B), of the present invention, having in the molecule thereof one or more reactive silicon groups and a functional group capable of reacting with the reactive groups of the component (A), those compounds each having the above described functional group can be used without any particular constraint.
• examples of the component (B) may include compounds each having a mercapto group and one or more reactive silicon groups, and compounds each having a hydrosilyl group represented by the following general formula and one or more reactive silicon groups: H—(Si(R 3 2-a ) (X a )O) m Si(R 4 3-b )X b (5) wherein R 3 and R 4 represent the same or different alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or triorganosiloxy groups represented by (R′) 3 SiO—, and when two or more R 3 or R 4 are present, they may be the same or different; herein, R′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R′ groups may be the same or different; X represents a hydroxyl group or a hydrolyzable group, and when two or more or more
• hydrolyzable group as X described above, and any hydrolyzable groups well known in the art may be used.
• hydrolyzable groups may include: a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group.
• alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group are preferable because of the moderate hydrolyzability and easy handlability.
• hydroxy and hydrolyzable groups can be bonded, and (b+ ⁇ a) is preferably 1 to 5.
• those groups may be the same or different.
• Specific examples of the compound represented by the general formula (5) may include: halogenated silanes such as trichlorsilane, methyldichlorsilane, dimethylchlorsilane, phenyldichlorsilane, trimethylsiloxymethylchlorsilane and 1,1,3,3-tetramethyl-1-bromodisiloxane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane and trimehtylsiloxydiethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, trimethylsiloxymethylacetoxysilane and trimethylsiloxydiacetoxysilane; ketoximatesilanes such as
• each of the hydrolyzable groups X in the obtained terminal silyl groups can be converted into another hydrolyzable group Y.
• X is a halogen atom
• hydrogen halide having strong irritating odor is generated in curing with moisture, and accordingly it is preferable to convert such an X group into another hydrolyzable group.
• the hydrolyzable functional group which can be adopted in such conversion may include an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group and a mercapto group.
• Various methods for converting the halogen functional groups into these hydrolyzable groups may be cited.
• specific examples of the methods for conversion into an alkoxy group may include the methods in which a halogen functional group is reacted with the following sets of compounds: (1) alcohols and phenols such as methanol, ethanol, 2-methoxyethanol, sec-butanol, t-butanol and phenol; (2) sodium alkoxide, potassium alkoxide, lithium alkoxide, and the like of alcohols and phenols; (3) orthoformates such as methyl orthoformate and ethyl orthoformate; and (4) epoxy compounds such as ethylene oxide, propylene oxide and allyl glycidyl ether.
• alcohols and phenols such as methanol, ethanol, 2-methoxyethanol, sec-butanol, t-butanol and phenol
• sodium alkoxide, potassium alkoxide, lithium alkoxide, and the like of alcohols and phenols (3) orthoformates such as methyl orthoformate and ethyl orthoformate; and (4) epoxy compounds
• the reactions concerned can be easily carried out, to yield satisfactory results, by use of a reaction system based on a combination of (1) and (3) composed of alcohols, phenols and orthoformates, and a reaction system based on a combination of (1) and (4) composed of alcohols, phenols and epoxy compounds.
• specific examples of the methods for conversion into an acyloxy group may include the methods in which a halogen functional group is reacted with carboxylic acids such as acetic acid and propionic acid; acid anhydrides such as acetic anhydride; and sodium salts, potassium salts and lithium salts of carboxylic acids.
• specific examples of the methods for conversion into an aminooxy group may include the methods in which a halogen functional group is reacted with hydroxylamines such as N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-methylphenylhydroxylamine and N-hydroxylpyrrolidine; and sodium salts, potassium salts and lithium salts of hydroxylamines.
• hydroxylamines such as N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-methylphenylhydroxylamine and N-hydroxylpyrrolidine
• specific examples of the methods for conversion into an amide group may include the methods in which a halogen functional group is reacted with primary and secondary amines such as N,N-dimethylamine, N,N-diethylamine, N-methylphenylamine and pyrrolidine; and sodium salts, potassium salts and lithium salts of primary and secondary amines.
• specific examples of the methods for conversion into an acid amide may include the methods in which a halogen functional group is reacted with acid amides having at least one hydrogen atom on the nitrogen atom such as acetamide, formamide and propionamide; and sodium salts, potassium salts and lithium salts of the aforementioned acid amides.
• reaction systems based on the combinations of ketoximes such as acetoxime and methyl ethyl ketoxime with orthoformates or epoxy compounds and the use of the reaction systems based on the combinations of mercaptans such as N-octylmercaptan and t-butylmercaptan with orthoformates or epoxy compounds respectively can result in a partial conversion into ketoximate groups and a partial conversion into mercapto groups, and the remaining parts can be converted into alkoxyl groups derived from the orthoformates or the epoxy compounds.
• the polymer concerned can be used after not only the halogen functional groups are converted into other hydrolyzable functional groups as described above, but also various hydrolyzable functional groups are converted into other hydrolyzable functional groups.
• the group VIII transition metal catalyst effectively used is the complex catalyst of a metal selected from the group VIII transition metals such as platinum, rhodium, cobalt, palladium and nickel.
• a metal selected from the group VIII transition metals such as platinum, rhodium, cobalt, palladium and nickel.
• the group VIII transition metal catalyst is particularly preferably any one of H 2 PtCl 6 .6H 2 O, a platinum-vinylsiloxane complex, a platinum-olefin complex from the viewpoint of the hydrosilylation reactivity.
• the hydrosilylation reaction is favorably carried out within a temperature range usually from 10 to 150° C., preferably from 20 to 120° C., and more preferably from 40 to 100° C.; according to the needs such as the adjustment of the reaction temperature and the adjustment of the viscosity of the reaction system, there may be used solvents such as benzene, toluene, xylene, tetrahydrofuran, methylene chloride, pentane, hexane and heptane.
• solvents such as benzene, toluene, xylene, tetrahydrofuran, methylene chloride, pentane, hexane and heptane.
• AlCl 3 , TiCl 4 and the like may also be used in addition to the aforementioned ones.
• the hydrosilylation reaction may be carried out in the presence of an antioxidant.
• the compound having a mercapto group and one or more reactive silicon groups in the molecule thereof may include: ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane and ⁇ -mercaptopropylmethyldiethoxysilane.
• the compound concerned is not particularly limited to these examples.
• an organic compound having, for example, an isocyanate group as a functional group capable of reacting with the component (A) and other compounds may be cited as the component (B).
• examples of such a compound may include: ⁇ -isocyanatepropyltrimethoxysilane, ⁇ -isocyanatepropylmethyldimethoxysilane ⁇ -isocyanatepropyltriethoxysilane and ⁇ -isocyanatepropylmethyldiethoxysilane.
• the compound concerned is not limited to these examples.
• an organic compound having, for example, an amino group as a functional group capable of reacting with the component (A) and other compounds may be cited as the component (B).
• a compound may include: ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldiethoxysilane, ⁇ -ureidopropyltrime
• the method for introducing reactive silicon groups into the polyoxyalkylene polymer (A) preferable is a method in which a polyoxyalkylene polymer, as the component (A), having alkenyl groups is reacted with a compound, as the component (B), having a hydrosilyl group in the molecule thereof, because the viscosity of the thus obtained, reactive silicon group-containing polyoxyalkylene polymer becomes relatively low.
• the organic compound having one or more reactive silicon groups and a functional group capable of reacting with the reactive groups in the polyoxyalkylene polymer (A)
• a polyoxyalkylene polymer (A) having a molecular weight distribution of 1.6 or less, a number average molecular weight of 15,000 to 50,000, and 0.8 or more of reactive groups, on average, per molecule thereof
• the proportion of the organic compound is preferably 0.8 to 1.5 molecules thereof, on average, per molecule of the component (A).
• the proportion When the proportion is less than 0.8 molecule, the amount of the polyoxyalkylene polymers, having no reactive silicon groups introduced thereinto and providing the cause for staining, is increased, while when the proportion exceeds 1.5 molecules, the cured product obtained unpreferably exhibit high modulus and low elongation.
• the amount of the component (B) to be reacted with one molecule of the component (A) is preferably 1.0 to 1.4 molecules of the component (B); it is particularly preferably 1.0 to 1.3 molecules because the curability and the mechanical properties as a sealant can be ensured, and the amount of the polyoxyalkylene polymers, having no reactive silicon groups introduced thereinto and providing the cause for staining, can be decreased.
• a modified polymer of the reactive silicon group-containing polyoxyalkylene polymer which is obtained by reacting the polyoxyalkylene polymer (A) having a molecular weight distribution of 1.6 or less, a number average molecular weight of 15,000 to 50,000, and 0.8 or more of reactive groups, on average, per molecule thereof with the organic compound (B) having in the molecule thereof one or more reactive silicon groups and a functional group capable of reacting with the reactive groups of (A) in a proportion of 0.8 to 1.5 molecules of the organic compound (B), on average, per molecule of the component (A).
• the typical modified polymers is a polymer which is obtained, in the presence of a polyoxyalkylene polymer having the reactive silicon groups, by polymerizing a mixture composed of an alkyl (meth)acrylate monomer represented by the following general formula (6) and containing an alkyl group having 1 to 8 carbon atoms and/or alkyl (meth)acrylate monomer represented by the following general formula (7) and containing an alkyl group having 10 or more carbon atoms and/or an alkyl (meth)acrylate monomer represented by the following general formula (8) and containing a reactive silicon group.
• an alkyl (meth)acrylate monomer represented by the following general formula (6) and containing an alkyl group having 1 to 8 carbon atoms and/or alkyl (meth)acrylate monomer represented by the following general formula (7) and containing an alkyl group having 10 or more carbon atoms and/or an alkyl (meth)acrylate monomer represented by the following general formula (8) and containing a reactive silicon
• the blends in which the polymers of (6), (7) and (8) are blended with the reactive silicon group-containing oxyalkylene polymer may also be used: CH 2 ⁇ C(R 5 )COOR 6 (6) wherein R 5 represents a hydrogen atom or a methyl group, and R 6 represents an alkyl group having 1 to 8 carbon atoms; CH 2 ⁇ C(R 5 )COOR 7 (7) wherein R 5 is the same as above, and R 7 represents an alkyl group having 10 or more carbon atoms; and CH 2 ⁇ C(R 5 )COOR 8 —[Si(R 3 2-a )(X a )O] m Si(R 4 3-b )X b (8)
• R 5 is the same as above
• R 8 represents a divalent alkylene group having 1 to 6 carbon atoms
• R 3 , R 4 , X, a, b and m are the same as described above.
• R 6 in the above general formula (6) may include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a n-butyl group, a t-butyl group and a 2-ethylhexyl group.
• the monomers represented by the general formula (6) may be used each alone or in combinations of two or more thereof.
• R 7 in the above general formula (7) may include long-chain alkyl groups having 10 or more carbon atoms, usually 10 to 30 carbon atoms, and preferably 10 to 20 carbon atoms, such as a lauryl group, a tridecyl group, a cetyl group, a stearyl group and a biphenyl group.
• the monomers represented by the general formula (7) may be used each alone or in combinations of two or more thereof.
• R 8 in the above general formula (8) may include groups having 1 to 6 carbon atoms and preferably 1 to 4 carbon atoms, such as a methylene group, an ethylene group and a propylene group.
• Examples of the reactive silicon groups to be bonded to R 8 may include a trimethoxysilyl group, a methyldimethoxysilyl group, a triethoxysilyl group and a methyldiethoxysilyl group.
• the monomers represented by the general formula (8) may be used each alone or in combinations of two or more thereof.
• monomers other than those represented by formulas (6), (7) and (8) may be concomitantly used.
• examples of such monomers may include: acrylic acids such as acrylic acid and methacrylic acid; amide group-containing monomers such as acrylamide, methacrylamide, N-methylolacrylamide and N-methylolmethacrylamide; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; amino group-containing monomers such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; and monomers such as acrylonitrile, styrene, ⁇ -methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate and ethylene.
• the ratio of the total amount of the polymerized monomers of formulas (6), (7) and (8) to the total amount of the polymerized monomers may include: acrylic acids
• the ratio y/x is 0.4, there is a fear that uncrosslinked liquid component bleeds from the cured product to provide a cause for staining.
• the ratio y/x is more preferably 0.3 or less; it is particularly preferably 0.2 or less for the purpose of ensuring the anti-staining property.
• the component having at least one reactive silicon group means a polyoxyalkylene polymer into which one or more reactive silicon groups are introduced when the component (A) is reacted with the component (B), while the component having no reactive silicon groups means a polyoxyalkylene polymer having no reactive silicon groups introduced when the component (A) is reacted with the component (B), and in the case where the curable composition of the present invention contains a plasticizer, it includes the plasticizer component and the polyoxyalkylene polymer having no reactive silicon groups.
• a plasticizer may be added to the curable composition of the present invention.
• plasticizer may include: phthalates such as dioctyl phthalate and diisodecyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate; epoxidized plasticizers such as epoxidized soybean oil and epoxidized flaxseed oil; polyethers such as polypropylene glycol and the derivatives thereof; and vinyl polymers obtained by polymerizing vinyl monomers by means of various methods. These plasticizers may be used each alone or in combinations of two or more thereof.
• the used amount of a plasticizer is preferably 10 parts by weight or less in relation to 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer obtained by reacting the component (A) with the component (B).
• the used amount is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less; for the purpose of ensuring the anti-staining property, it is particularly preferable that no plasticizers are added. It may be noted that the curable composition of the present invention can ensure a sufficient workability even when no plasticizers are added thereto because the reactive silicon group-containing polyoxyalkylene polymer is low in viscosity.
• the filler (C) of the present invention is not limited to any specific fillers.
• Specific examples of the filler (C) may include: reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; fillers such as calcium carbonate, magnesium carbonate, diatomite, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, active zinc white, and organic fillers including hydrogenated castor oil, PVC and polyolefin; fibrous fillers such as asbestos, glass fiber and glass filament; inorganic balloons and organic balloons such as shirasu balloon, glass balloon, Saran balloon and phenolic balloon; one or more of these fillers may be used according to need.
• the used amount of the filler(s) is preferably 1 to 200 parts by weight, and particularly preferably 5 to 200 parts by weight in relation to 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer obtained by reacting the component (A) with the component (B).
• the curing catalyst (D) in the present invention is the curing catalyst capable of accelerating the reaction of the reactive groups of the reactive silicon group-containing polyoxyalkylene polymer obtained by reacting the component (A) and the component (B), in the curable composition, with each other.
• the curing catalyst (D) may include: titanium esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin diacetylacetonate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; lead octylate; amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, banzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine,
• the used amount of the curing catalyst(s) is preferably approximately 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight in relation to 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer obtained by reacting the component (A) with the component (B).
• adhesion-imparting agents may be added according to need.
• adhesion-imparting agents may include: amino group-containing silanes such as ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -ureidopropyltriethoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltrimethoxysilane and ⁇ -anilinopropyltrimethoxysilane; mercapto group-containing silanes such as ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxy
• the solvents may include nonreactive solvents such as hydrocarbons, acetates, alcohols, ethers and ketones. No particular constraint is imposed on the solvents as long as they are such solvents as described above.
• additives may include: antisagging agents such as hydrogenated castor oil, organic bentonite and calcium stearate; colorants; antioxidants; ultraviolet absorbers; and photostabilizers.
• antisagging agents such as hydrogenated castor oil, organic bentonite and calcium stearate
• colorants such as hydrogenated castor oil, organic bentonite and calcium stearate
• antioxidants such as antioxidants; ultraviolet absorbers; and photostabilizers.
• additives such as adhesion improvers, physical property adjusters, storage stability improvers, lubricants, pigments and foaming agents may also be added optionally according to need.
• the method for producing the curable composition of the present invention which includes the reactive silicon group-containing polyoxyalkylene polymer obtained by reacting the component (A) and the component (B) with each other, the component (C) and the component (D); there may be adopted common methods such as, for example, a method in which the above described components are combined and kneaded with a mixer, roll, kneader or the like, and a method in which the individual components are dissolved by use of a solvent and mixed together.
• the composition concerned may also be prepared as either a one-component composition or a two-component composition.
• Propylene oxide was polymerized by use of a polyoxypropylene diol having a number average molecular weight of 2000 as initiator and a double metal cyanide complex as catalyst, to yield a polyoxypropylene diol which has a number average molecular weight of 30200 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.2.
• a polyoxypropylene diol which has a number average molecular weight of 30200 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.2.
• To this product 2 parts by weight of a 30% methanol solution of sodium methylate was added, and thereafter devolatilization was carried out at 130° C. under reduced pressure until no methanol was recovered. Subsequently, 1.3 parts by weight of allyl chloride was added and the reaction mixture was allowed to react for 5 hours.
• Propylene oxide was polymerized by use of a polyoxypropylene diol having a number average molecular weight of 2000 as initiator and a double metal cyanide complex as catalyst, to yield a polyoxypropylene diol which has a number average molecular weight of 30200 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.2.
• a polyoxypropylene diol which has a number average molecular weight of 30200 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.2.
• To this product 2 parts by weight of a 30% methanol solution of sodium methylate was added, and thereafter devolatilization was carried out at 130° C. under reduced pressure until no methanol was recovered. Subsequently, 1.6 parts by weight of methallyl chloride was added and the reaction mixture was allowed to react for 5 hours.
• Propylene oxide was polymerized by use of a polyoxypropylene diol having a number average molecular weight of 2000 as initiator and a double metal cyanide complex as catalyst, to yield a polyoxypropylene diol which has a number average molecular weight of 20500 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.2.
• a polyoxypropylene diol which has a number average molecular weight of 20500 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.2.
• To this product 2.5 parts by weight of a 30% methanol solution of sodium methylate was added, and thereafter devolatilization was carried out at 130° C. under reduced pressure until no methanol was recovered. Subsequently, 1.5 parts by weight of allyl chloride was added and the reaction mixture was allowed to react for 5 hours.
• Propylene oxide was polymerized by use of a polyoxypropylene diol having a number average molecular weight of 2000 as initiator and a double metal cyanide complex as catalyst, to yield a polyoxypropylene diol which has a number average molecular weight of 14300 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.1.
• a polyoxypropylene diol which has a number average molecular weight of 14300 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.1.
• 4.2 parts by weight of a 30% methanol solution of sodium methylate was added, and thereafter devolatilization was carried out at 130° C. under reduced pressure until no methanol was recovered.
• 2.8 parts by weight of allyl chloride was added and the reaction mixture was allowed to react for 5 hours.
• Propylene oxide was polymerized by use of a polyoxypropylene diol having a number average molecular weight of 2000 as initiator and a double metal cyanide complex as catalyst, to yield a polyoxypropylene diol which has a number average molecular weight of 30200 (as measured by GPC, relative to polystyrene standard) and a molecular weight distribution of 1.2.
• the obtained polypropylene glycol was added with 0.6 mol of ⁇ -isocyanatepropyltrimethoxysilane in relation to 1 mol of the hydroxyl groups of the obtained polypropylene glycol, and the reaction mixture was subjected to urethanation reaction to yield a polyoxyalkylene polymer (P16) having trimethoxysilyl groups at the terminals thereof.
• a curable composition was prepared by fully kneading a mixture composed of 120 parts by weight of P8 obtained in Synthesis Example 8 as the reactive silicon group-containing polyoxyalkylene polymer, 120 parts by weight of calcium carbonate as filler, 2 parts by weight of dibutyltin bisacetylacetonate as curing catalyst, 20 parts by weight of titanium oxide, 5 parts by weight of polyamide wax, 2 parts by weight of vinyltrimethoxysilane, and 3 parts by weight of N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane. The following tests were carried out by use of the curable composition thus obtained.
• a curable composition was prepared in the same manner as in Example 1 except that 6 parts by weight of a polyoxypropylene diol having a number average molecular weight of 3000 was used as plasticizer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P12 obtained in Synthesis Example 12 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P7 obtained in Synthesis Example 7 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P9 obtained in Synthesis Example 9 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P16 obtained in Synthesis Example 16 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P11 obtained in Synthesis Example 11 was used as the reactive silicon group-containing polyoxyalkylene polymer, and 36 parts by weight of a polyoxypropylene diol having a number average molecular weight of 3000 was used as plasticizer.
• the evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P6 obtained in Synthesis Example 6 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P10 obtained in Synthesis Example 10 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P13 obtained in Synthesis Example 13 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P14 obtained in Synthesis Example 14 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• a curable composition was prepared in the same manner as in Example 1 except that 120 parts by weight of P15 obtained in Synthesis Example 15 was used as the reactive silicon group-containing polyoxyalkylene polymer. The evaluations of the obtained composition were carried out in the same manner as in Example 1.
• the curable composition of the present invention is satisfactory in workability, gives the cured product obtained therefrom satisfactory in anti-staining property, and has mechanical properties desirable for sealant.
• the curable composition of the present invention can be effectively used as sealants for use in building construction providing suppressed staining around joints and also for other applications.

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